Monoazo dyestuffs insoluble in water



j {UNITED- STATES ATETf OFFICE Patented Aug. 6, 1940 y l I I 2,210,072 I MONOAZO DYESTUFFS INSOLUBLE DI I WATER Ernst Fischer, ofienbach-on-the -Main, Germany,

' 'fassignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application February 21, 1939, Se-

rial 15101251763; In Germany February 23,

5Claims. (Cl.260-- 203) The present invention relates to monoazo dye- R3 and R4 Stand f y -u a a y n a ylor hystufis insoluble in water; more particularly it droar ma ic radi als which m y be nnected relates tddyestuffs of the following general forin' a h er cyclic rmg' ys em, and wherein the mula: i naphthalene radical may contain as substituent R1 in the nucleus b an alkoxy-group or halogen and 5 the benzene radical 0 may contain alkyl, alkoxy, 1 v v a i aralkoxy-,' aryloxy-groups or halogen atoms, only R1 such dyestufi' components being used as do not contain any group lending solubility in water,

The new dyestuffs yield orange to violet shades of'good propertiesoffastness, They are insol-- a ublevin Water, but very easily soluble inmany Lb/ organic solvents, such as hydrocarbons, alcohols, esters, ketones, and can, thereforabe used for l 1 r v Q v j coloring these solvents as well as the lacquers wherein X rand Y stand for one of the groups 1 p ep d y a s of these s t h a 30 d .s0 R1, 2 Rs-and t d=: nitroor acetyl-celluloselacquers, films or plasfor alkyl, aralkyl, aryl or hydroaromatic radia tic m se They are alsovery suitable for colorl hi h may b n t d in'a heterocycliql ing;varnishes, candles and fats. Owing to the ring system, wherein thebenzene radicals it and different Substitlleflts Present in h y the 0 may contain further alkyl-, alkoxy-,'aralkoxyj-,- suitability of the organic solvents named varies; aryloXyf-groups or halogen atoms and. wherein", mosfiysuitable' Solvents V e y the naphthalene radical may contain as sub be f 6 by e p t- I I stituent in the nucleus'b an alkoxy-group or? In comparison with the dyestuffs described in halogen, French Patent No. 749,926, the dyestufis obtain- I have found that valuable pigment dyestuffs-.2 a e by i i v n are distinguished y their are obtainable coupling a, diazo-compound Hconsiderably better solubilityv in organic solvents from an amine of the general formula: "so that they are especially suitable for coloring -substances oi? the above kind, whereas the dye- 1 stuffs of the said patent have a solubility too g v l small for these purposes.v NHz\/ The following examplesserve to illustrate the V 7 invention, but they are not intended to limit it wherein X stands for the group ,CO or. s02,'R1 and R2 stand for a1kyl-, aralkyl .15.7 parts of 1-amino-2-methoxybenzene-baryl- .or hydroaromatic radicals which may bet y n-dibutylamine) are diaz'otized in the connected n xheterocyclic ring'system, andfiT-usual manner; In orderto bind theeXceSs of wherein the benzene radical a may contain ,fure '-':mineral acid,v sodium acetate is added to the ther alkyl-, alkoxy-, aralkoxyor aryloxyegroups diazo-solution and the whole is then introduced, o h o en atoms, w an arylidenf d XY f 'While stirring, into-asolution @242 parts of 2.3- p fih m acid of f i g?' hydroxynaphthoyl-l=amino-2"-methoxybenzenegeneral formulm 5,-(sulfonyl-n-dibutylamine) in diulte ,'caustic soda solution. When the coupling is complete, 45

fj the' dyestufi formed is' filtered, with suction,,' washed well and dried. It is-a-red powderwhich uneasily-dissolves in acetone, ethyl alcohol and otherv-,,-v;.crganic solvents. and colorsv'celluloseJester lac- 1 Whereiri means the roup 4G0; at "hea ff I I such as a sulfonic or carboxylic'acid group. m

thereto; the parts are by. weight:

quers vivid bluish-red tints of good properties of fastness. The dyestuff corresponds with the S OLN S O2.N

' CO.NH

OCHa

other organic solvents and colors nitroand acetyl-cellulose lacquers as well as varnishes vivid red tints which are much more yellowish than those obtainable with the product of Example 1. I

3. If there are used in Example 1 instead of benzylamine) and 22.7 parts 15.7 parts of 1-amino-2-methoXybenzene-5-(sulfonyl-n-dibutylamine), 9.6 parts of l-aminobenzenei-(carbonyl-diethylamine), a dyestuff having similarly good properties of fastness is obtained; it colors the various organic solvents and the lacquers prepared therewith as well as candles and fats yellowish-red tints.

4. A pigment dyestufi is prepared in the manner described in Examples 1 and 2 from 17.3 parts of 1 amino-2-methoxybenzene-5-(carbonyl-diof 2.3-hydroxynaphthoyl-l aminobenzene-l (sulfonyl-n-dibutylamine). It dissolves easily in butyl acetate and xylene and colors varnishes and nitroor acetylcellulose lacquers red tints of good fastness to light.

5. From the diazo-compound of 11.? parts of l-amino- 2 -methoxybenzene- -(carbonyl-N-piperidine) and 23.4 parts of 2.3-hydroxynaphthoyl- 1'-amino- 2 -methoxtybenzene- 5 'Acarbonyl-N- (n) -butyl-phenylamine) there is obtained, in the manner described in Examples 1 and 2, a red dyestuil' which dissolves easily in organic solvents and colors plastic masses and lacquers prepared therewith as well as candles and fats bluish-red tints of good fastness to light.

The following table comprises a number of other monoazo dyestuffs obtainable by this invention which are likewise easily soluble in the solvents usual for these purposes and have good properties of fastness.

2-methoxybenzene-5-(carbonyl-N -carbazo1e) Diazo-compound from Coupled with Shade 213-hydroxynaphthoyl-1-amino- 1 l-aminobenzene-Zl-(sulphonyl-diethylamine) Benzene-4-(sulphonyl-n-dibutylamme) Orange. 2 l-amino 2-methylbenzene 5 (sulphonyl-N (n )butyldo YellowiSh-red,

[2 -methyl-] phenylamine). v 3 1-:i11min1o-2-me;;hy1benzene-5-(sulphonyl-N-benzyl-cyclo- 2'-ethoxybenzene-5-(sulphonyl-n-dibutylamine) Red,

exy amine 4 l-amino-iethoxybenzene-S-(sulphonyl-n-dibutylamine) 2'-methylbenzene-5- (sulphonyl-n-d1butylamme) Bluish-red 5 l-amino-4-chlor0benzene-5-(sulphonyl-diethylamine) 2-me thylbenzene-5-(sulphonyl-N-(n-)butyl-phenyl- Red.

amine. 6 l-aminogzbenzyloxybenzenep (sulphonyl n dibutyl 2-methylbenzene-5-(sulphonyl-diethylamine) D amine 7 1-amin0-4-phei10xybenzene-5-(sulphonyl-n-dibutylamjne) Benzene-4-(sulphonyl-dlethylamme) Do. 8 l-aminobenzene-l-(sulphonyl-n-dibutylamine) Benzene-3-(sulphonyl-N-methyl-phenylamme) Orange. 9 l-aminos2. 5- dimeth0xy-benzene-4- (sulphonyl-n-dibutyl- 2-methoxyb enzene5-(sulphonyl-n-dibutylamine) Bordea amine 10 1-aminobenzene-4-(carbonyl-N-(n-) butyl-phenylamine) Red. 11 l-aniinobenzene-B-(carbonyl-N-(n-) butyl-phenylamine) D0. 12 1 amino 7 2 methylbenzene 5 (carbonyl N (n -)butyl Do.

plienylamme). 13 1- amino 2-methoxybenzene- 5- (carbonyl-N- (n -)butyl Bluish-red.

phenylamine). 14 l-amino; zzs-dimethoxybenzene- 4- (carbonyl-ndibutyl- 2'-methoxybenzene-5-(sulphonyl-n-dibutylamine) Red-violet,

amine 15 1-iminf-amethoxybenzene-5-(carbonyl-N-ethyl-cyclo- 2'-metlioxybenzene-5-(sulphonyl-N-piperidine) Bluish-red exy amine 16 l-amino-2-methoxybenzene-5-(carbonyl-N-benzyl-phenyl- 4'-methoxybenzene-5-(sulphonyl-n-dibutylamine) BIDIII l7 l-aminobenzcne-B-(carbonyl-dicyclohexylamine) 4 -meth)y1benzene 5 (sulphonyl -N methyl bcnzyl- Red.

amine 18 1-aminobenzene-3-(carbonyl-diplienylamine) 2-methylbenzene-5-(sulphonyl-n dibutylamine) D 19 l-amino-2-methylbenzene-5-(carbonyl-diphenylamine) .1 Benzene-3-(sulphonyl dibutylamine) D 20 1-amino-2-methoxyb enzene-5-(carbonyl-diphenylamine) 2-methoxybenzene-5-(sulphonyl-n dibutylam ne) B1 i h. 21 l-agiinol- 2- methoxybenzene- 5- (carbonyl-N -(n-)buty1- 2-methoxybenzene-5-(sulphonyl-dimethylamme) D p eny amine 22 d0 Benzeney-(sulphonyl-N-ethyl-cyclohexylamine) W Red. 23 1-amino-2-methoxybenzene-5-(carbonyl-diisobutylamine) 2-ch1orobenzene-4-(sulplionyl-dietliylamine) 1 D 24 1-amino-2-ethoxybenzene-5- (carbonyl-n-dibutylamine) Benzene-4J-(sulplionyl-dibenzylamine) i D 25 1-agnifio-z-nrgethoxybenzene-5- (carbonyl-N-etliyl-1-naph- 2-methoxybenzene-5-(carbonyl-N-piperidine) finishd,

t y amine 26 1-amino-2-methoxybenzene-5-(carbonyl-N-carbazole) 2'-methoxybenzene-5-(carbonyl-n-dibuty1amine) D 27 l-amino-Z-methylbenzene-d (sulphonyl-n-dibutylamine) 2- me)thoxybenzene-5-(carbonyl-N-benzyl-phenyl-ani- Red.

me 28 1- aminoi2. 5-dimethoxy-benzene-4- (sulphonyl-ndibutyl- 2'-methoxybenzene-5- (carbonyl-dicyclohexylamine) B rdea x amine 29 l-aminoi-ethoxybenzene-d(sulphonyl-n-dibutylamine) 2-methylbenzene-5-(carbonyl-diphenylamine) Red. 30 l-amino-Z-metliylb enzene-5-(carbonyl-diphenylainine) Benzene-2 -(carb0nyl-dib0nzy1amin 1 1 Yellowish ed, 31 l-amino-2-methylbenzene-5-(sulfonyldimethylamine) Benzene-2'-(sulfonyl-N-benzyl-cyclohexylamine) Red. 32 l-amino52-methoxybenzene-5-(sulfonyl-N-methyl-benzyldo Do.

amine 33 l-aigiinoi2.5;diethoxybenzene-4- (carbonyl-N- (n) -bi1tyl- Benzenei-(carbonyl-diethy1amine) Red-violet,

p eny amine 34 l-amino-Z-methoxybenzene-5-(sulfonyl-n-dibutylamine) 2'-phenoxybenzene-5-(sulfonyl-diethy1am1ne) Red. 35 -do 2'-benzyloXybenzene-5-(sulionyln-dibutylamine) D 36 do 2-me tlio)Xybenzene-5-(carb0nyl-N-ethyli-1-naplithyl- Do,

amine 37 l-amino-2-methoxy-5-methylbenzene-4-(carbonyl-N-(n)- Benzene-4'-(carbonyl-N-(n)-butyl-phenylamine) Bluish-red.

butyl-phenylamine) 38 1-amino-2-methoxybenzene-5-(sulfonyl-n-d1butylamine) Red.

kind the process can be conducted in the same manner.

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims, do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid p.

I claim: 1. The water-insoluble monoazo dyestuifs of the following general formula:

Z2 /R1 Zx -X.N\

OH /Ra Y.N\ OO.NH R

wherein X and Y stand for one of the groups CO and -SO2, R1, R2, R3 and R4 stand for members of the group consisting of alkyl-, benzyl-, aryland hydroaromatic radical which may be connected to form a heterocyclic ring system, Z1 and Z3 stand for members of the group consisting of hydrogen, alkyl, alkoxy, benzyloxy, phenoxy and halogen, Z2 and Z; for members of the group consisting of hydrogen, alkyl and alkoxy and b for a member of the group consisting of hydrogen, alkoxy and halogen, being insoluble in water, but very easily soluble in organic solvents and yielding orange to violet shades of good properties of fastness.

Diem-compound from- Qoupled with- Shade 39 1-a1 1 1ino 2.5 di%thoxy-henzene-4-(carbonyl-N-(n)-butyl- 4'-methyl-5 (sulfonyl-diethylamine) Red-violet.

p enyamine. 1 40 n 2-methyl-5-(sulfonyl-N-methyl-benzylauune) Do. 41 l-fllfillIlO-fi.5-qlniethoxyEbenzelle-i-(calbollyl-N-(131)-b11ty1- 2-methoxybenzene-5-(sulionyl-diethylamme);; Do.

penymme. 42 l-ammobenzene-3-(carbonyl-dicyclohexylamine)if Benzene-4-(sulfonyl-n-dibutylamme)- Yellowish red 43 l-amino-2-methoxybenzene-5-(sulfonyl-n-dibutylamine) 4-methoxybenzene-6-(sulfonyl-N-morpliolinc) Red. 44 1-a1nin i{2-nethoxybenzene-5-(carbonyl-N-tetrahydro- 2'.5-dimethoxybenzene-4-(sulionyl- -d1butylamin Do.

qumo ne 45 1-amino-4-methoxybenzene-5-(sulionyl-N-morpholine) 2'.4-dimethoxybenzene-5'-(sulfonyl-n-dibutylamine) i Do. 46 l-afiinolz-meiihoxybenzene- 5 (carbonyl-N (n) -butyl- 2-methoxybenzene-6-(carbonyl-diethylamme) Do.

p eny amine 47 1-amino-3-methoxybenzene-G-(carbonyl-diethylamine) 2.5-dimethoxybenze1ie=4-(sulfonyl-n-dibutylamine) Do. 48 do I 2.4-d1methoxybenzcne-5-(sulfonyl- -dibutylamine) Do. 49 l-amino-iethoxybenzene-fi-(sulfonyl-n-dibutylamine) do Bluish-red. 50 l-ajmtiniri-metihoxy:fiimethyl-benzenei-(carbnyl-N-(n)- Benzene-4'-(carbonyl-N-(n)-butyl-phenylamme) Red.

uyp enyamine." 51 l-amino-2-methoxy'benzene-5- (sulfonyl-n-dibutylamine) 2'.4-dimetl1ylbcnzene-5- (carbonyl-n-dibutylamine) Do.

I 6-metl1oxy-2.3-hydroxynaphthoyl-1'-am1no- 52 I-aEfinoI-Z-meghoxybenzene--(carbonyl-N-(n)-butyl- 2-methoxybenzene-5-(sulfonyl-diethylamme) Bordeaux.

p eny amme g 53 1-am ino)-2.5-dimethoxy-benzenei-(carbony-n-dibutyldo Vlolet.

' amine. 1 g 54 1-amino)-2.5-dimetl1oxy-benzene-4-(sulfonyl-n-dibutyl- 2,-methylbcnzene-5-(sulfonyl-diethylamine) Red-violet. amine 55 do 2-methylbenzene-5-(carbonyl-n-dibutylamine) Do. 56 l-amino-2-methoxybenzene-5-(carbonyl-diphenylamme) 2-methoxybenz ene-5-(sultonyl-n-dibutylamme) Bordeaux.

57 1-amino-2.5-dimethoxybenzene-4-(carbonyl-N-(n)-butyl- .do 0 Violet. j phenylamine). 58 l-al lniiio2-mthoxybenzene-5-(carbonyl-N-ethyl-1-naph- 2-methylbenzene-5-(sulfonyl-u-dlbutylamme). Bordeaux.

1: amine y 6-bromo-2.3-hydroxynaphthoy1-1'-amino- 59' l-amino-2-methoxybenzene-5-(carbonyl-diisobutylamme) 2-methoxybenzene-5-(sulfonyl-diethylamine) Bluish-red. 60 1-amino-2-methoxyb enzene-5-(carbonyl-diisobutylamlne) 2-methylbenzene'-5'-(carbonyl-n-dlbutylamine) Do.

With other bases 0r naphthols of the above 2. The water-insoluble monoazo dyestuffs of the following general formula:

wherein X and Y stand for one of the groups CO- and SO2-, R1, R2, R3 and R4 stand for members of the group consisting of alkyl-, benzyl-, aryland hydroaromatic radical which may be connected to form a heterocyclic ring system, Z and Z1 stand for members of the group consisting of hydrogen, alkyl, alkoxy, benzyloxy, phenoxy and halogen, being insoluble in water, but very easily soluble in organic solvents and yielding orange to violet shades of good prop- .erties of fastness.

3. The water-insoluble monoazo dyestufi' of the following formula:

S 0:.N (n) C4119 CHaO R C4110 N S Oz.N (n) C4Ho OH O O .NH

being a red powder which dissolves easily in organic solvents, such as acetone, ethyl alcohol,

butyl acetate, ethyl acetate, butyl alcohol and xylene, and colors, for instance, cellulose ester lacquers vivid bluish red tints of good properties of fastness.

4. The water-insoluble monoazo dyestufi of the following formula:

being a red powder which dissolves easily in organic solvents, such as acetone, ethyl alcohol, butyl acetate, ethyl acetate, butyl alcohol and Xylene, and colors, for instance, cellulose ester lacquers vivid red tints of good properties of fastness.

5. The water-insoluble monoazo dyestuff of the following formula:

being a red powder which dissolves easily in organic solvents, such as acetone, ethyl alcohol, 20 butyl acetate, ethyl acetate, butyl alcohol and xylene, and colors, for instance, cellulose ester lacquers vivid red tints of good properties of fastness.

ERNST FISCHER. 25 

